Long lasting disinfectant cleaning compositions and methods of use thereof

ABSTRACT

The present disclosure provides an antimicrobial composition that includes: an antimicrobial component having at least one quaternary ammonium compound; a synthetic polymer that includes: at least one cationic monomer A b , optionally, at least one anionic monomer B a , and optionally, at least one non-ionic monomer C a ; an organic acid; and a surfactant selected from cationic surfactants, amphoteric surfactants and combinations thereof; and at least one non-ionic surfactant selected from the group consisting of low hydrophilic-lipophilic balance (HLB) non-ionic surfactants with a delocalized electronic structure that have moderate to poor water solubility. This composition when applied to a surface demonstrates good cleaning ability and provides robust long lasting disinfection.

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims the benefit of priority under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 62/804,923, filed onFeb. 13, 2019, the entire disclosure of which is incorporated herein byreference.

BACKGROUND

Antimicrobial compositions commercially available as disinfectants or ascleaners with disinfecting activity typically achieve bacterial or viralkill at 99.9% or greater only at the time of use. Re-contamination ofthe “clean” surface allows microorganisms to survive and spread throughcontact until it is treated again. The disinfection-cleaner market doesnot currently address long lasting disinfection for high contact areasincluding homes, public areas and healthcare environments. This hascreated demand with modern, health-conscious consumers who care about aclean home but do not have the time to clean and disinfect on a regularbasis.

The critical technical challenge for developing a long lastingdisinfectant cleaning composition is that while cleaning requires thepresence of effective surfactants for soil removal, the presence of suchsurfactants reduces the durability or the long lasting nature of theresidual film. Deterioration of the residual disinfectant film makes itextremely difficult to achieve 12 to 24 hour continuous disinfection.

Re-soiling or contamination of the surface requires additionaltreatments with such compositions. A need, therefore, exists fordisinfectant cleaning formulations that provide high microbial killwithout the need for repeated applications. However, designingcompositions that meet the above requirements is a difficult task inview of unpredictable and complicated interactions between ingredients.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is flow chart depicting the RSS-12h analysis conducted in theExamples;

FIG. 2 provides a frame of reference for reconciling the cleaningapplication to desired performance;

FIG. 3 shows inadequate cleaning performance of a long lastingdisinfectant (Formulation A pH 4.5);

FIG. 4 shows the impact of varying amounts of TSP-8EO on cleaningperformance;

FIG. 5 shows the impact on cleaning of a formulation containing a blendof TSP-4EO and TSP-8EO as compared to Benchmark A;

FIG. 6 demonstrates an embodiment in which substrate wetting wasimproved with removal of lactic acid; and

FIG. 7 shows the impact on cleaning of various non-ionic surfactants.

SUMMARY

The present disclosure provides hard surface treatment compositions thatinclude an antimicrobial component including at least one quaternaryammonium compound; a synthetic polymer including: at least one cationicmonomer A_(b), optionally, at least one anionic monomer B_(a), andoptionally, at least one non-ionic monomer C_(a); an organic acid; asurfactant selected from cationic surfactants, amphoteric surfactantsand combinations thereof; and at least one non-ionic surfactant selectedfrom low hydrophilic-lipophilic balance (HLB) non-ionic surfactants witha delocalized electronic structure that have moderate to poor watersolubility. Also presented are methods of providing a surface withresidual antimicrobial action that include the step of applying acomposition of the present disclosure to the surface. The presentdisclosure also provides a substrate with residual antimicrobial actioncomprising a substrate wherein at least a portion of the substrate iscoated with a composition of the present disclosure.

DETAILED DESCRIPTION

The present disclosure relates to cleaning compositions that providecontinuous surface disinfection benefit for 12 to 24 hours with only oneapplication, obviating the need for repeated decontamination. Thecleaning efficacy of these compositions is provided by inclusion of lowhydrophilic-lipophilic balance (HLB) non-ionic surfactants withdelocalized electronic structure that have moderate to poor watersolubility. Such disinfectant cleaning compositions provide a residualfilm that is abrasion resistant to wet and dry wipes while providinglong lasting disinfection.

The present compositions achieve microorganism (e.g. bacterial, viral,or fungal) kill of at least 95% or greater, (e.g. 99.9% kill), for 12 to24 hours obviating the need for repeated treatment. In order tosubstantiate 24 hour long-term sanitization claims with the UnitedStates Environmental Protection Agency (EPA), compositions are evaluatedwith the residual self-sanitization (RSS) method, EPA Protocol #01-1A(https://www.epa.gov/sites/production/files/2015-09/documents/cloroxpcol_final.pdf).For validating longer term disinfection, all extant test protocolsemulate the maximum amount of recontamination and abrasion by touchingand wiping anticipated before reapplication, typically a 24 hour period.An intermediate protocol with approximately half the level abrasion andre-soiling challenge to a surface is presented here as the “RSS-12h”test protocol.

In an embodiment, a film formed from the composition kills at least99.9% (e.g. log 3 reduction) of microorganisms according to the residualself-sanitizing (RSS) activity test (EPA Protocol #01-1A). In anembodiment, a film formed from the composition kills at least 99.9%(e.g. log 3 reduction) of gram-positive bacteria and gram-negativebacteria according to the residual self-sanitizing (RSS) activity test(EPA Protocol #01-1A).

Long lasting disinfection claims are substantiated by the RSS test,which challenges the applied composition by subjecting it torecontamination (re-inoculation with microorganisms) and abrasion (wearcycles). An intermediate test protocol, with approximately half thenumber of re-inoculations and wear cycles (“RSS-12h”) is used to predictdisinfection that is durable up to 12 hours before reapplication of thetest product. As outlined in FIG. 1, this procedure requires preparationof the test bacterial (microbial) culture over the first week (see EPAProtocol #01-1A) followed by testing in week 2.

The testing involves inoculating the surface with bacteria, followed byapplication of the product on the substrate and allowing it to dry. Thesubstrate may be glass, polycarbonate, or steel. This substrate is thensubjected to an abrasion—re-inoculation regime of 3 “wear cycles”. Theabrasion is conducted with a 1084 gwt. rectangular steel block coveredwith a cloth with an underlying thin polyurethane-foam layer. Each wearcycle is composed of a “dry” abrasion and a “wet” abrasion, the latterwith the cloth cover having been wet with a mist of water using aPreval® sprayer. Each abrasion (dry/wet) is characterized by a back andforth motion of the block across the test substrate. Each abrasion cycleis followed by re-inoculation the surface with a bacterial culture. TheRSS-12h involves a 3-abrasion cycle/3-inoculations test as compared tothe full RSS test that outlines a 6-abrasion cycle/6-inoculation testregimen. All other details of the test method are as outlined in the EPAProtocol #01-1A.

The test substrate is allowed to dry overnight and then finallyinoculated again (sanitizer test) for 5 minutes, followed byneutralization of the entire substrate. Surviving bacteria is thenharvested off the surface and cultured with serial dilutions on agarplates, allowing colony formation over 24-48 hours. Surviving bacteriaare then counted as the number of colonies. The difference in bacterialcount inoculated and surviving bacteria results in an efficacyevaluation in percent kill (e.g. 99.9% kill) or log-reduction (e.g.3-log reduction) on a logarithmic scale. The bacteria in this test maybe substituted for other microorganisms such as fungi or viruses. In anembodiment, microorganisms are selected from gram-positive bacteria (e.gStaphylococcus aureus), gram-negative bacteria (e.g. Enterobacteraerogenes), fungi, enveloped viruses, non-enveloped viruses, andcombinations thereof.

The composition of the present disclosure is a liquid formulation. It iscontemplated that one preferred method of making use of the compositionof the present disclosure is to apply a layer of the composition to asubstrate and dry the composition or allow it to dry. The act ofapplying a layer of the composition to a substrate and then drying it orallowing it to dry is known herein as “treating” the substrate. It iscontemplated that, as the solvent evaporates, the composition will forma film on the substrate. The dried layer of the composition is knownherein as “a film.”

In an embodiment, the composition includes: an antimicrobial componentthat includes at least one quaternary ammonium compound; a syntheticpolymer that includes: at least one cationic monomer A_(b), optionally,at least one anionic monomer B_(a), and optionally, at least onenon-ionic monomer C_(a); an organic acid; a surfactant selected fromcationic surfactants, amphoteric surfactants and combinations thereof;and at least one non-ionic surfactant selected from the group consistingof low HLB non-ionic surfactants with a delocalized electronic structurethat have moderate to poor water solubility. In an embodiment, thecomposition includes two or more (e.g. three, four, five, etc.)non-ionic surfactants selected from the group consisting of low HLBnon-ionic surfactants with a delocalized electronic structure that havemoderate to poor water solubility.

In an embodiment, the non-ionic surfactant(s) is/are selected from thegroup consisting of non-ionic surfactants with a delocalized electronicstructure having an HLB value less than 9. In an embodiment, thenon-ionic surfactant(s) is/are selected from the group consisting ofnon-ionic surfactants with a delocalized electronic structure having anHLB value less than 8. In an embodiment, the non-ionic surfactant(s)is/are selected from the group consisting of non-ionic surfactants witha delocalized electronic structure having an HLB value less than 7. Inan embodiment, the non-ionic surfactants possess a combination ofdifferent HLB values. In an embodiment, the low HLB non-ionic surfactantwith a delocalized electronic structure that has moderate to poor watersolubility is selected from the group consisting of tristyrylphenolethoxylates, terpene alkoxylates, alkanolamides, and combinationsthereof. In an embodiment, the low HLB non-ionic surfactant with adelocalized electronic structure that has moderate to poor watersolubility is selected from the group consisting of amine surfactants.In an embodiment, the non-ionic surfactant is a tristyrylphenolethoxylate with a low degree of ethoxylation (e.g. less than eightethylene oxide (EO) moieties).

In an embodiment, the pH of the composition ranges from about 0 to about5.5. In another embodiment, the pH of the composition is less than 5.5.In another embodiment, the pH of the composition ranges from 2 to 4.9.In yet another embodiment, the pH of the composition ranges from 3 to4.8. In an embodiment, the pH of the composition ranges from 0.5 to 3.

The antimicrobial compositions of the present disclosure include atleast one quaternary ammonium compound. In an embodiment, the quaternaryammonium compound is an antimicrobial “quat.” The term “quaternaryammonium compound” or “quat” generally refers to any composition withthe following formula:

where R1-R4 are alkyl groups that may be alike or different, substitutedor unsubstituted, saturated or unsaturated, branched or unbranched, andcyclic or acyclic and may contain ether, ester, or amide linkages; theymay be aromatic or substituted aromatic groups. In an embodiment, groupsR1, R2, R3, and R4 each have less than a C20 chain length. X⁻ is ananionic counterion. The term “anionic counterion” includes any ion thatcan form a salt with quaternary ammonium. Examples of suitablecounterions include halides such as chlorides, bromides, fluorides, andiodides, sulphonates, propionates, methosulphates, saccharinates,ethosulphates, hydroxides, acetates, phosphates, carbonates,bicarbonates, and nitrates. In an embodiment, the anionic counterion ischloride.

In some embodiments, quaternary ammoniums having carbon chains of lessthan 20 or C2-C20 are included in compositions of the presentdisclosure. In other embodiments, quaternary ammoniums having carbonchains of C6-C18, C12-C18, C12-C16 and C6-C10 are included incompositions of the present disclosure. Examples of quaternary ammoniumcompounds useful in the present disclosure include, but are not limitedto, alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethylbenzylammonium chloride, octyl decyl dimethyl ammonium chloride, dioctyldimethyl ammonium chloride, and didecyl dimethyl ammonium chloride. Asingle quaternary ammonium or a combination of more than one quaternaryammonium may be included in compositions of the present disclosure.Further examples of quaternary ammonium compounds useful in the presentdisclosure include, but are not limited to, benzethonium chloride,ethylbenzyl alkonium chloride, ethyl benzethonium chloride, myristyltrimethyl ammonium chloride, methyl benzethonium chloride, cetalkoniumchloride, cetrimonium bromide (CTAB), carnitine, dofanium chloride,tetraethyl ammonium bromide (TEAB), domiphen bromide, benzododeciniumbromide, benzoxonium chloride, choline, denatonium, and mixturesthereof.

In some embodiments depending on the nature of the R group, the anion,and the number of quaternary nitrogen atoms present, the antimicrobialquaternary ammonium compounds may be classified into one of thefollowing categories: monoalkyltrimethyl ammonium salts;monoalkyldimethylbenzyl ammonium salts; dialkyldimethyl ammonium salts;heteroaromatic ammonium salts; polysubstituted quaternary ammoniumsalts; bis-quaternary ammonium salts; and polymeric quaternary ammoniumsalts. Each category will be discussed herein.

Monoalkyltrimethyl ammonium salts contain one R group that is along-chain alkyl group, and the remaining R groups are short-chain alkylgroups, such as methyl or ethyl groups. Some non-limiting examples ofmonoalkyltrimethyl ammonium salts include cetyltrimethylammoniumbromide, commercial available under the tradenames Rhodaquat® M242C/29and Dehyquart® A; alkyltrimethyl ammonium chloride, commerciallyavailable as Arquad® 16; alkylaryltrimethyl ammonium chloride; andcetyldimethyl ethylammonium bromide, commercially available as Ammonyx®DME.

Monoalkyldimethylbenzyl ammonium salts contain one R group that is along-chain alkyl group, a second R group that is a benzyl radical, andthe two remaining R groups are short-chain alkyl groups, such as methylor ethyl groups. Some non-limiting examples of monoalkyldimethylbenzylammonium salts include alkyldimethylbenzyl ammonium chlorides,commercially available as Barquat® from Lonza Inc.; and benzethoniumchloride, commercially available as Lonzagard®, from Lonza Inc.Additionally, the monoalkyldimethylbenzyl ammonium salts may besubstituted. Non-limiting examples of such salts includedodecyldimethyl-3,4-dichlorobenzyl ammonium chloride. Finally, there aremixtures of alkyldimethylbenzyl and alkyldimethyl substituted benzyl(ethylbenzyl) ammonium chlorides commercially available as BTC® 2125Mfrom Stepan Company, and Barquat® 4250 from Lonza Inc. Other examplesinclude N,N-benzyldimethyloctylammonium chloride,N,N-benzyldimethyldecylammonium chloride,N-dodecyl-N-benzyl-N,N-dimethylammonium chloride,N-tetradecyl-N-benzyl-N,N-dimethyl ammonium chloride,N-hexadecyl-N,N-dimethyl-N-benzylammonium chloride, N,N-dimethylN-benzyl N-octadecyl ammonium chloride.

Dialkyldimethyl ammonium salts contain two R groups that are long-chainalkyl groups, and the remaining R groups are short-chain alkyl groups,such as methyl groups. Some non-limiting examples of dialkyldimethylammonium salts include didecyldimethyl ammonium halides, commerciallyavailable as Bardac® 22 from Lonza Inc.; didecyl dimethyl ammoniumchloride commercially available as Bardac® 2250 from Lonza Inc.; dioctyldimethyl ammonium chloride, commercially available as Bardac® LF andBardac® LF-80 from Lonza Inc.; and octyl decyl dimethyl ammoniumchloride sold as a mixture with didecyl and dioctyl dimethyl ammoniumchlorides, commercially available as Bardac® 2050 and 2080 from LonzaInc.

Heteroaromatic ammonium salts contain one R group that is a long-chainalkyl group, and the remaining R groups are provided by some aromaticsystem. Accordingly, the quaternary nitrogen to which the R groups areattached is part of an aromatic system such as pyridine, quinoline, orisoquinoline. Some non-limiting examples of heteroaromatic ammoniumsalts include cetylpyridinium halide, commercially available as Sumquat®6060/CPC from Zeeland Chemical Inc.;1-[3-chloroalkyl]-3,5,7-triaza-1-azoniaadamantane, commerciallyavailable as Dowicil® 200 from The Dow Chemical Company; andalkyl-isoquinolinium bromide.

Polysubstituted quaternary ammonium salts are a monoalkyltrimethylammonium salt, monoalkyldimethylbenzyl ammonium salt, dialkyldimethylammonium salt, or heteroaromatic ammonium salt wherein the anion portionof the molecule is a large, high-molecular weight (MW) organic ion. Somenon-limiting examples of polysubstituted quaternary ammonium saltsinclude alkyldimethyl benzyl ammonium saccharinate, anddimethylethylbenzyl ammonium cyclohexyl sulfamate.

Bis-quatemary ammonium salts contain two symmetric quaternary ammoniummoieties having the general formula:

where the R groups may be long or short chain alkyl, a benzyl radical orprovided by an aromatic system. Z is a carbon-hydrogen chain attached toeach quaternary nitrogen. Some non-limiting examples of bis-quaternaryammonium salts include 1,10-bis(2-methyl-4-aminoquinoliniumchloride)-decane; and 1,6-bis[1-methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethylammonium chloride] hexane or triclobisoniumchloride.

In an embodiment, the quaternary ammonium compound is a medium to longchain alkyl R group, such as from 8 carbons to about 20 carbons, from 8carbons to about 18 carbons, from about 10 to about 18 carbons, and fromabout 12 to about 16 carbons, and providing a soluble and goodantimicrobial agent.

In an embodiment, the quaternary ammonium compound is a short di-alkylchain quaternary ammonium compound having an R group, such as from 2carbons to about 12 carbons, from 3 carbons to about 12 carbons, or from6 carbons to about 12 carbons.

The composition may include from about 100 to about 20,000 ppm of one ormore quaternary ammonium compounds. In various embodiments, thecomposition includes from about 500 to about 20,000 ppm; from about 500to about 10,000 ppm; from about 100 to about 500 ppm; or from about 500to about 5000 ppm of one or more quaternary ammonium compounds.

Polymers suitable for use in compositions of the present disclosureinclude synthetic polymers having: at least one cationic monomer A_(b),optionally, at least one anionic monomer B_(a), and optionally, at leastone non-ionic monomer C_(a). In one embodiment, the synthetic polymerincludes its homopolymer, copolymer, terpolymer, block copolymer, randompolymer, linear polymer, comb polymer or branched polymer.

Any combination of these types of monomers may be used. For example,suitable polymers include but are not limited to those comprising,consisting of or consisting essentially of at least one monomer of typeA_(b) and at least one monomer of type B_(a) and polymers comprising,consisting of or consisting essentially of at least one monomer of typeA_(b) and at least one momoner of type C_(a), and polymers comprising,consisting of or consisting essentially of at least one of each of thethree types of monomer.

In an embodiment the cationic monomer A_(b) includes an ammonium groupof formula —NR3+, wherein R, which is identical or different, representsa hydrogen atom, an alkyl group comprising 1 to 10 carbon atoms, or abenzyl group, optionally carrying a hydroxyl group, and comprise ananion (counter-ion). Examples of anionic counter-ions are halides suchas chloride and bromides, sulphates, hydrosulphates, alkylsulphates (forexample comprising 1 to 6 carbon atoms), sulfonates, phosphates,nitrates, citrates, carbonates, bicarbonates, formates, and acetates.

Examples of cationic monomer A_(b) include, but are not limited to:

Diallyldimethylammonium halides such as diallyldimethylammonium chloride(DADMAC) or the corresponding bromide. Alternatively, the counter ionmay be sulphate, nitrate or phosphate. Similar momomer units, such asthose in which one or more of the CH₃ groups is replaced by aC_(2 to 12) for example a C_(2 to 6) alkyl group or one or more of theCH₂ groups is replaced by an alkyl group having from 2 to 12, forexample from 2 to 6 carbon atoms may be used. In other words, othersimilar commercially available monomers or polymers containing suchmonomers may be used.

N,N,N-trimethyl-3-((2-methyl-1-oxo-2-propenyl)amino)-1-propanaminiumhalides, such as the chloride (MAPTAC, also known asmethacryl-amido(propyl)-trimethyl ammonium chloride).

Additional examples of cationic monomer A_(b) include, but are notlimited to:

1. aminoalkyl (meth)acrylates, aminoalkyl (meth)acrylamides,

2. monomers, including particularly (meth)acrylates, and(meth)acrylamides derivatives, comprising at least one secondary,tertiary or quaternary amine function, or a heterocyclic groupcontaining a nitrogen atom, vinylamine or ethylenimine;

3. diallyldialkyl ammonium salts;

4. their mixtures, their salts, and macromonomers deriving fromtherefrom;

5. dimethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acrylate, ditertiobutylaminoethyl (meth)acrylate,dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl(meth)acrylamide;

6. ethylenimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine;

7. trimethylammoniumethyl (meth)acrylate chloride, trimethylammoniumethyl (meth)acrylate methyl sulphate, dimethylammonium ethyl(meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammonium ethylacrylate chloride, trimethyl ammonium ethyl (meth)acrylamido (alsocalled 2-(acryloxy)ethyltrimethylammonium, TMAEAMS) chloride,trimethylammoniumethyl (meth)acrylate (also called2-(acryloxy)ethyltrimethylammonium, TMAEAMS) methyl sulphate, trimethylammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethylammonium chloride,

8. diallyldimethyl ammonium chloride,

9. monomers having the following formula A(II):

wherein R₁ is a hydrogen atom or a methyl or ethyl group; R₂, R₃, R₄, R₅and R₆, which are identical or different, are linear or branched C₁-C₆,preferably C₁-C₄, alkyl, hydroxyalkyl or aminoalkyl groups; m is aninteger from 0 to 10, for example 1; n is an integer from 1 to 6,preferably 2 to 4; Z represents a —C(O)O— or —C(O)NH— group or an oxygenatom; A represents a (CH₂)_(p) group, p being an integer from 1 to 6,preferably from 2 to 4; B represents a linear or branched C₂-C₁₂,typically C₃-C₆, polymethylene chain optionally interrupted by one ormore heteroatoms or heterogroups, in particular O or NH, and optionallysubstituted by one or more hydroxyl or amino groups, preferably hydroxylgroups; X, which are identical or different, represent counterions, andtheir mixtures, and macromonomers deriving therefrom.

Other cationic monomers include compounds of general formula A(I):

in which: R₁ and R₄, independently of each other, represent a hydrogenatom or a linear or branched C₁-C₆ alkyl group; R₂ and R₃, independentlyof each other, represent an alkyl, hydroxyalkyl or aminoalkyl group inwhich the alkyl group is a linear or branched C₁-C₆ chain, preferably amethyl group; n and m are integers between 1 and 3; X, which may beidentical or different, represent counterions which are compatible withthe water-soluble or water-dispersible nature of the polymer. In oneembodiment, X is selected from the group of halide anions, sulfateanions, hydrogen sulfate anions, phosphate anions, nitrate anions,citrate anions, formate anions, or acetate anions.

The polymers used in the present invention may have a polyampholytestructure such that the charge and surface adsorption are determined bypH. In an embodiment, the polymer is an acrylic acid amine-functionalpolymer. Examples of suitable hydrophilic polymers are described in U.S.Pat. Nos. 6,569,261, 6,593,288, 6,703,358 and 6,767,410, the disclosureof these documents is incorporated herein by reference. These documentsdescribe water-soluble or water-dispersible copolymers including, in theform of polymerized units, (1) at least one amine-functional monomer,(2) at least one hydrophilic monomer with an acidic nature and (3)optionally at least one neutral hydrophilic monomer having an ethylenicunsaturation. The copolymers include quaternized ammonium acrylamideacid copolymers.

Examples of the anionic monomer B_(a) include, but are not limited to,acrylic acid, methacrylic acid, α-ethacrylic acid, β,β-dimethacrylicacid, methylenemalonic acid, vinylacetic acid, allylacetic acid,ethylideneacetic acid, propylideneacetic acid, crotonic acid, maleicacid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid,N-methacryloylalanine, N-acryloylhydroxyglycine, sulfopropyl acrylate,sulfoethyl acrylate, sulfoethyl methacrylate, sulfoethyl methacrylate,styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid,phosphoethyl acrylate, phosphonoethyl acrylate, phosphopropyl acrylate,phosphonopropyl acrylate, phosphoethyl methacrylate, phosphonoethylmethacrylate, phosphopropyl methacrylate and phosphonopropylmethacrylate, and the ammonium and alkali metal salts of these acids.

Examples of the non-ionic monomer C_(a) include, but are not limited to,alkyl acrylate; 2-(Dimethylamino)ethyl methacrylate (DMAEMA),

N-vinyl pyrrolidone (NVP), N-vinylimidazole, acrylamide, and

methacrylamide.

An example of a polymer suitable for use in the composition of thepresent disclosure is a polymer comprising, consisting of or consistingessentially of DMAEMA, MAPTAC and methylacrylic acid.

Suitable polymers include those sold under the trade name Mirapol®, forexample as Mirapol® Surf-SHO, Mirapol® Surf-S110, Mirapol® HSC-310,Mirapol® CP-412, Mirapol® Surf-5200 or Mirapol® Surf-5500 available fromSolvay, Novecare.

Other suitable polymers include polymers comprising, consisting of orconsisting essentially of DADMAC and acrylamide, such as those soldunder the trade name Polyquat® 7 or PQ7 from Surfacare or under thetrade name Merquat® S from Lubrizol. Other suitable polymers includepolymers comprising, consisting of or consisting essentially of DADMACand methacrylamide and/or, acrylic acid or methacrylic acid.

Polymers comprising, consisting of or consisting essentially of MAPTACand acrylamide or methacrylamide are also suitable for use in thecomposition of the present disclosure. Also suitable are polymerscomprising, consisting of or consisting essentially of MAPTAC and vinylpyrrolidone, such as Polyquat® 28. Suitable polymers include those soldunder the trade names Polyquart® Pro. (which is polyquat 28 plussilicone) and Polyquart® Ampo 140 from BASF.

Other suitable polymers include polymers comprising, consisting of orconsisting essentially of MAPTAC and acrylic acid or methacrylic acid,such as those sold under the trade name Polyquat® Ampho, eg Polyquat®Ampho 149.

Polymers comprising, consisting of or consisting essentially of DMAEMAand vinylpyrrolidone are suitable for use in the composition of thepresent disclosure. An example of such a polymer is sold under the namePQ11 by BRB International.

Other suitable polymers include polymers comprising, consisting of orconsisting essentially of DMAEMA and acrylamide, such as the polymersold under the trade name Polyquat® 5.

In an embodiment, the molecular weight of the polymer ranges from about130,000 g/mol to about 2 million g/mol.

In an embodiment, the amount of polymer in the composition ranges fromabout 200 ppm to about 4,000 ppm.

Compositions of the present disclosure further include one or moreorganic acids. In an embodiment, the organic acid is selected fromcitric, malic, maleic, oxalic, glutaric, succinic, lactic, glycolic,fumaric, acetic, benzoic, propionic, sorbic, tartaric, formic andmixtures of one or more such organic acids. In another embodiment, thecounterion acid may be polymeric acid, such as, for example,poly(acrylic acid) or other polycarboxylic acids (e.g. maleic anhydride,methacrylic acid, etc.) or homopolymers or copolymers (e.g. methylmethacrylate, butyl acrylate, etc.) thereof, such as those in theRhodoline® series available from Solvay. The composition may includefrom 500 to 7,000 ppm of one or more organic acids.

In compositions of the present disclosure, the surfactant is selectedfrom cationic surfactants, amphoteric surfactants and combinationsthereof. Cationic surfactants are surfactants that dissolve in water toresult in a net cationic charge. In an embodiment, when present, thecationic surfactant is selected from cationic amine oxides, cationicbetaines, propionates, amphoacetates and combinations thereof. Amineoxides, propionates, amphoacetates and betaines are cationic in theacidic pH conditions of the present disclosure. In an embodiment, thepropionate is selected from cationic C8-C22 propionates and saltsthereof. In another embodiment, the cationic C8-C22 propionate isselected from alkyl ampho(di)propionate, alkyl aminopropionates, alkylamphopropionates, salts thereof, and combinations thereof. In anembodiment the cationic amphoacetate is selected from amphoacetatesaccording to the following formula:

and diamphoacetates according to the following formula:

where R is an aliphatic group of 8 to 18 carbon atoms, and M is a cationsuch as sodium, potassium, ammonium, or substituted ammonium. Sodiumlauroamphoacetate, sodium cocoamphoacetate, disodium lauroamphoacetate,and disodium cocoamphodiacetate are preferred in some embodiments.

In an embodiment, the betaine is selected from cationic C8-C22 betainesand salts thereof. In a further embodiment, the cationic C8-C22 betaineis selected from alkyl dimethylbetaines, alkylamidopropyl betaines,alkylampho(di)acetates, salts thereof, and combinations thereof. Wherereference is made herein to “salts thereof” for cationic surfactants,these may be any suitable salts. In one embodiment the salt is a saltbased on a monovalent cation, such as Na, K, or NH₄. In one embodiment,the salt is a salt based on an alkali metal, e.g. Na or K. The use ofalternative salts, e.g. alkali earth metal salts such as Ca and Mg couldalso be contemplated; however the solubility of the product would needto be borne in mind when using such salts.

Amphoteric surfactants contain both a basic and an acidic hydrophilicgroup and an organic hydrophobic group. In an embodiment, when present,the amphoteric surfactant is selected from sultaines, taurates, andcombinations thereof. In an embodiment, the composition includes acombination of one or more cationic and amphoteric surfactants.

In addition to the components described herein, the composition may alsoinclude a polar carrier solvent (e.g. water), chelating agent,fragrance, preservative, dye, corrosion inhibitor, builder, cleansingsolvent and other components known to be useful in antimicrobialcompositions.

The compositions according to the present disclosure include bothdisinfectant cleaning compositions and concentrates which only differ inthe relative proportion of water to that of the other constituents. Theconcentrate can be used without dilution (concentrate:water 1:0) toextremely dilute dilutions (e.g., 1:10,000). In an embodiment, a rangeof dilution is from about 1:1 to about 1:1,000. In another embodiment, arange of dilution is from about 1:1 to about 1:500. In yet anotherembodiment, a range of dilution is from about 1:10 to about 1:128.

Also disclosed are methods of providing a surface with residualantimicrobial action that includes the step of applying a composition ofthe present disclosure to the surface.

The composition may be applied to a surface by any method, includingmethods conducted by hand and methods conducted by machine andcombinations thereof. For example, composition may be applied byspraying (pump, aerosol, pressure, etc.), pouring, spreading, metering(for example, with a rod or bar), mopping, wiping, brushing, dipping,mechanical application, other application methods, or combinationthereof.

In an embodiment, compositions of the present disclosure are suited foruse in a “spray and wipe” application. In such an application, the usergenerally applies an effective amount of the cleaning composition usingthe pump and within a few moments thereafter, wipes off the treated areawith a rag, towel, or sponge, usually a disposable paper towel orsponge.

Compositions of the present disclosure, whether as described herein orin a concentrate or super concentrate form, can also be applied to ahard surface by using a wet wipe. The wipe can be of a woven ornon-woven nature. Fabric substrates can include non-woven or wovenpouches, sponges, in the form of abrasive or non-abrasive cleaning pads.Such fabrics are known commercially in this field and are often referredto as wipes. Such substrates can be resin bonded, hydroentangled,thermally bonded, meltblown, needlepunched, or any combination of theformer.

The non-woven fabrics may be a combination of wood pulp fibers andtextile length synthetic fibers formed by well-known dry-form or wet-layprocesses. Synthetic fibers such as rayon, nylon, orlon and polyester aswell as blends thereof can be employed. The wood pulp fibers shouldcomprise about 30 to about 60 percent by weight of the non-woven fabric,preferably about 55 to about 60 percent by weight, the remainder beingsynthetic fibers. The wood pulp fibers provide for absorbency, abrasionand soil retention whereas the synthetic fibers provide for substratestrength and resiliency.

The compositions of the present disclosure are absorbed onto the wipe toform a saturated wipe. The wipe can then be sealed individually in apouch which can then be opened when needed or a multitude of wipes canbe placed in a container for use on an as needed basis. The container,when closed, sufficiently sealed to prevent evaporation of anycomponents from the compositions.

Also provided are substrates with residual antimicrobial action thatinclude a substrate wherein at least a portion of the substrate iscoated with a composition of the present disclosure. The formulation ofthe present disclosure may be put to use by application any substrate.Some suitable substrates include, for example, countertops, mirrors,sinks, toilets, light switches, doorknobs, walls, floors, ceilings,partitions, railings, computer screens, keyboards, instruments, etc.Suitable substrates may be found in various settings including, forexample, food preparation areas, households, industrial settings,architectural settings, medical settings, sinks, toilets, etc.Substrates may be made of any material; some suitable substratecompositions include, for example, plastic (including, for example,laminates and wall coverings), Formica, metal, glass, ceramic tile,paper (such as, for example, wallpaper), fabric, finished or unfinishedwood, etc.

Also provided is the use of a composition of the present disclosure tosubstantially reduce or control the formation of microbial colonies onor at a surface. In an embodiment, a film formed from the compositionkills at least 95% of microorganisms for at least 3 abrasion cyclesaccording to RSS-12h. In another embodiment, a film formed from thecomposition kills at least 95% of microorganisms according toEnvironmental Protection Agency (EPA) Protocol #01-1A residualself-sanitizing activity test (e.g. 6 abrasion cycles for a 24 hourclaim). In another embodiment, a film formed from the composition killsat least 99.9% of microorganisms for at least 3 abrasion cyclesaccording to RSS-12h. In yet another embodiment, a film formed from thecomposition kills at least 99.9% of microorganisms according toEnvironmental Protection Agency (EPA) Protocol #01-1A residualself-sanitizing activity test (e.g. 6 abrasion cycles for a 24 hourclaim).

In an embodiment, a film formed from the composition kills at least 95%of gram-positive bacteria and gram-negative bacteria, fungi, orenveloped and non-enveloped viruses for at least 3 abrasion cyclesaccording to RSS-12h. In another embodiment, a film formed from thecomposition kills at least 95% of gram-positive bacteria andgram-negative bacteria, fungi, or enveloped and non-enveloped virusesaccording to Environmental Protection Agency (EPA) Protocol #01-1Aresidual self-sanitizing activity test (e.g. 6 abrasion cycles for a 24hour claim). In another embodiment, a film formed from the compositionkills at least 99.9% of gram-positive bacteria and gram-negativebacteria, fungi, or enveloped and non-enveloped viruses for at least 3abrasion cycles according to RSS-12h. In yet another embodiment, a filmformed from the composition kills at least 99.9% of gram-positivebacteria and gram-negative bacteria, fungi, or enveloped andnon-enveloped viruses according to Environmental Protection Agency (EPA)Protocol #01-1A residual self-sanitizing activity test (e.g. 6 abrasioncycles for a 24 hour claim).

While specific embodiments are discussed, the specification isillustrative only and not restrictive. Many variations of thisdisclosure will become apparent to those skilled in the art upon reviewof this specification.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which this specification pertains.

As used in the specification and claims, the singular form “a”, “an” and“the” includes plural references unless the context clearly dictatesotherwise.

As used herein, and unless otherwise indicated, the term “about” or“approximately” means an acceptable error for a particular value asdetermined by one of ordinary skill in the art, which depends in part onhow the value is measured or determined. In certain embodiments, theterm “about” or “approximately” means within 1, 2, 3, or 4 standarddeviations. In certain embodiments, the term “about” or “approximately”means within 50%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%,0.5%, or 0.05% of a given value or range.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

The present disclosure will further be described by reference to thefollowing examples. The following examples are merely illustrative andare not intended to be limiting.

EXAMPLES

ASTM Procedure for Cleaning

The ASTM Method for Cleaning D4488 is intended for testing theperformance of products used on resilient flooring and washable walls.This method includes preparation of soil, set-up for cleaning andevaluation of performance under hard surface cleaning conditions. Astraight-line wash ability apparatus is used to clean surface. Thismethod is designed to be analogous to that of a surface that is soiledand then cleaned by a consumer. This test is used to test the cleaningefficacy of all types of multipurpose household cleaners.

Preparation of the Substrate: This test protocol calls for preparationof a double coated Masonite tiles with latex paint using a paint roller.This paint must be an interior acrylic flat white. The paint brand hasbeen predetermined by the customer to be highly porous to allowabsorption of the soil. The ASTM method traditionally calls forCalifornia Paints Brand that has since been discontinued. The tiles arethen set to dry for 24 hours at 45° C. prior to any soil application.The next day the center test area is marked off with a pencil at about3.5″ length to show boundaries of where the soil needs to be appliedwith a cheesecloth.

Preparation of Cheesecloth: A cheesecloth is used to apply the soil ontothe substrate. The cheesecloth should be cut to 18″×36″dimensions andthen folded in half several times to finally provide with a 2.5″×2″piece that is locked into a large 2″ binder clip.

Sponge Preparation: A cellulose sponge is used for the cleaning of thesoil on the surface. The sponge is cut into 4 pieces to fit snug intothe sponge box of the wear tester and as described below. The spongesare then thoroughly washed and squeezed to semi-dry prior to anyapplication of product.

Preparation of Soil: A blend of 33% vegetable shortening is combinedwith 33% lard, 33% vegetable oil and 1% carbon black. Soil is made freshby warming the mixture for 30 minutes at 75° C. and applied 24 hoursprior to testing.

Application of Soil to Substrate: Once the blend of oils and carbonblack is heated and homogenous, it can be applied to the substrate withthe cheesecloth while maintaining constant heat and mixing. Thecheesecloth is soaked in the heated mixture for a few minutes to allowthe absorption into the cheesecloth and then applied at moderate speedfor a total of six strokes in a downward motion. The application of thesoil onto the substrate is applied perpendicular to the cleaningdirection of the scrubbing apparatus. The cheesecloth is dipped into theheated mixture between each stroke.

Cleaning Test: 15 g of the cleaner is pipetted evenly throughout thesurface of the cellulose sponge. It is then placed into a sponge box(Total weight ˜350 g) and placed onto the board that is clamped into thestraight-line washability apparatus. A predetermined number of cyclesand speed are established to allow the sponge to go over the surface ina consistent manner usually a total of 5 cycles.

Soil Blend Ratios: Initially when the wallboard cleaning method wasimplemented, the soil ratios of lard, oil, shortening and carbon blackdiffered from that of the ASTM method. The altered ratio (30% vegetableshortening; 30% lard; 30% vegetable oil; and 10% carbon black) wasinitially conducted due to test protocols with a greater amount ofcarbon black. Additional carbon black was used to visualize thedifference between various products tested. This could be due tomultiple factors such as particle size of the carbon black as well asits aggregation behavior with polymers in formulations.

Substrate Paint: As per ASTM Method the type of paint was specified tobe an acrylic flat white interior paint by California Paints (Item53300). An alternative flat white paint was used since the supplier nolonger produces that exact version that was outlined in the test methoddue to the lack of scrub resistance. It was determined that a Behr ProDead Flat Paint would be used going forward in testing.

Supplier of Carbon Black: The ASTM method calls for use of AcrosCarbonlamp, but since this exact grade has been discontinued, weexperimented with different types of carbon black. We identified a gradeof carbon black (Panther 405) which shows better variation of cleaningbetween different cleaning products.

Application of Soil: In the development stages of the cleaning protocolwe were using a 50 mil (1 mil=1/1000 inch) drawdown bar. The soil waspipetted parallel to the board on the top edge and was then flow coateddown with 1 stroke from the drawdown bar. We have since switched awayfrom this form of application to be more compliant to the ASTM protocol.

Comparative Example 1—Evaluation of Current Disinfectant CleaningBenchmarks

Ready-to-use trigger spray benchmarks readily available on the market asdisinfectant cleaners were tested for their cleaning performance withASTM D4488 wallboard cleaning test. All these products claim >99.9% killfor bacteria and viruses and are efficient disinfectants. However, it isclearly apparent that Benchmark A (“quat” based all-purpose cleaner—APC)is highly effective at removing the carbonaceous greasy soil, comparedto Benchmark B (bleach based APC), Benchmark C (citric acid basedbathroom cleaner—BC) and “Harsh Free” Benchmark D (peroxide based APC).None of these cleaner disinfectants provide long lastingcleaning-disinfection which would require passing the RSS-12h or RSS-24hprotocol. The disinfectant cleaners provide a frame of reference forreconciling the cleaning application to desired performance. (FIG. 2).

Comparative Example 2—Cleaning Efficacy of Long Lasting Disinfectant

The composition of long lasting disinfectant Formulation A is shown inTable 1. Films prepared from Formulation A were evaluated using RSS-12hprotocol with E. aerogenes as described above, a modified version theresidual self-sanitization (RSS) method, EPA Protocol #01-1A. All thefilms were prepared by pipetting 150 microliters of the formulation on a(1×1) inch steel substrate and allowed to air dry. Formulation Aprovides a robust formulation which passes RSS-12h with 4.82 LR (logreduction—greater than 3); it is a long lasting disinfectant.Formulation A has pH 4.5 with the additional lactic acid for pH controlas detailed below, at which the added amine oxide is cationic giving aclear and stable solution. Formulation A is free of non-ionicsurfactants.

TABLE 1 Components A (actives) (ppm) Alkyldimethylbenzylammoniumchloride 1960 (ADBAC) (CAS 68424-85-1) Dimethyldidecylammonium chloride7840 (DDAC) (CAS 7173-51-5) Mirapol ® Surf-S110 4000 Lactic acid 810Glutamic acid diacetic acid, tetrasodium 760 salt (GLDA) Decylamineoxide (e.g. Mackamine ® 2700 C10) Water Balance Test MicroorganismEnterobacter aerogenes Test Substrate Steel Log Reduction 4.82

Formulation A was further evaluated for cleaning performance by ASTMD4488 as described above and compared to the best performing cleaner,Benchmark A. As can be seen in FIG. 3, Formulation A performs poorlycompared to the cleaning efficacy of Benchmark A. Benchmark A removedroughly around 70% of the soil, whereas the Formulation A removedroughly 30%.

Example 3—Addition of Low HLB Tristyrylphenol Ethoxylate (TSP-xEO)

The addition of tristyrylphenol ethoxylate surfactants in Formulation Ashowed instant improvement in the dispersion of carbon black. The effecton cleaning performance of adding different levels of TSP-8EO toFormulation A (Table 2) while maintaining the composition at pH 4.5 wasstudied.

TABLE 2 Components A (Actives) (ppm) Alkyldimethylbenzylammonium 1960chloride (ADBAC) (CAS 68424-85-1) Dimethyldidecylammonium chloride 7840(DDAC) (CAS 7173-51-5) Mirapol ® Surf-S110 4000 Lactic acid 810 Glutamicacid diacetic acid, 760 tetrasodium salt (GLDA) Decylamine oxide (e.g.Mackamine ® 2700 C10) Tristyrylphenol ethoxylate - 8EO 2500-10000

The cleaning performance at different levels of added TSP-8EO is shownin FIG. 4. The addition of TSP-8EO drastically improves cleaning atlevels above 0.5%.

Example 4—Impact on RSS-12h of Varying Quat Levels

Formulation B (Table 3) was prepared using Mirapol® HSC-310, adjustingthe level of citric acid, and reducing the TSP-8EO. Formulation B showedvery similar cleaning to Benchmark A (FIG. 5), which is one of the mosteffective disinfectant cleaners on the market.

TABLE 3 Components B C (Actives) (ppm) (ppm) Alkyldimethylbenzylammonium1960 1960 chloride (ADBAC) (CAS 68424-85-1) Dimethyldidecylammoniumchloride 7840 7840 (DDAC) (CAS 7173-51-5) Mirapol ® HSC-310 400 400Citric acid 6720 6720 Lactic acid 810 — Glutamic acid diacetic acid, 760760 tetrasodium salt (GLDA) Decylamine oxide (e.g. Mackamine ® 2700 2700C10) Tristyrylphenol ethoxylate - 4EO 1000 1000 Tristyrylphenolethoxylate - 8EO 3500 3500 Water Balance Balance Test MicroorganismEnterobacter aerogenes Test Substrate Steel Steel Log Reduction TNTC4.55

The effect of minimizing acids on abrasion and RSS-12h was studied.Formulation B was further adapted to remove the lactic acid in thecomposition (Formulation C— Table 3) while maintaining the additionalmultivalent citric acid and GLDA. The removal of lactic acid from theformulation led to an interesting wetting pattern on steel tiles usedfor RSS-12h. Product dewetting to the corner was not observed, incontrast to what as was seen with Formulations A and B. In the absenceof lactic acid, the product was more wetting on the surface (FIG. 6).This improved wetting effect is desirable when testing for abrasionresistance and RSS-12h.

Samples of the above formulations were submitted for RSS-12h. Thesesamples included Formulations B and C with and without lactic acid.Formulation C (without lactic acid) showed 4.55 log reduction and passedRSS-12h. The achievement of greater than 3 log reduction provides adisinfectant-cleaner with a 12 hour claim for 99.9% residual killfollowing 3 wet and 3 dry abrasions. The cleaning efficacy was notimpacted due to the removal of lactic acid (Formulation C) where even atpH 4.0 the performance was equivalent to the market leading Benchmark Awhile providing long lasting disinfection.

In another embodiment, reduction of quat content was studied. It isdesirable to have the least amount of quats feasible to get acceptableresidue feel while achieving long lasting disinfection. Formulation D isa clear stable composition at half (5000 ppm) quat as shown in Table 4.

TABLE 4 Components D (actives) (ppm) Alkyldimethylbenzylammonium 1000chloride (ADBAC) (CAS 68424-85-1) Dimethyldidecylammonium chloride 4000(DDAC) (CAS 7173-51-5) Mirapol ® HSC-310 1200 Citric acid 3300 Glutamicacid diacetic acid, 760 tetrasodium salt (GLDA) Decylamine oxide (e.g.Mackamine ® 2700 C10) Tristyrylphenol ethoxylate - 4EO 1000Tristyrylphenol ethoxylate - 8EO 2000 Water Balance Test MicroorganismEnterobacter aerogenes Test Substrate Steel Log Reduction 3.99

Formulation D, showed 3.99 log reduction with the RSS-12h test. Theachievement of greater than 3 log reduction provides acleaner-disinfectant with a 12 hour claim for 99.9% residual killfollowing 3 wet and 3 dry abrasions. The cleaning efficacy was slightlyreduced due to the reduced quat. However, even at pH 4.0 the performanceof Formulation D was equivalent to most benchmarks (other than BenchmarkA) while providing long lasting disinfection.

Example 5—RSS-24h for Disinfectant Cleaners at Varying Quat Levels

RSS-24h performance was studied using Formulations E and F (Table 5).

TABLE 5 Components E F (actives) (ppm) (ppm) Alkyldimethylbenzylammoniumchloride 7840 1000 (ADBAC) (CAS 68424-85-1) Dimethyldidecylammoniumchloride 1960 4000 (DDAC) (CAS 7173-51-5) Mirapol ® HSC-310 3200 1600Citric acid 4803 3300 Glutamic acid diacetic acid, tetrasodium 760 760salt (GLDA) Dodecylamine oxide (e.g. Mackamine ® 2700 2700 LA)Tristyrylphenol ethoxylate - 4EO 1000 1000 Tristyrylphenol ethoxylate -8EO 3500 2000 Water Balance Balance Test Microorganism EnterobacterEnterobacter aerogenes aerogenes Test Substrate Steel Steel LogReduction 2.76 3.76

Formulation E is close to passing RSS-24h with 2.76 LR. Formulation Fdoes succeed in passing RSS-24h with 3.76 LR. The HLB of the mixednon-ionic surfactant (TSP-4EO+TSP-8EO) for Formulation F is less thanfor Formulation E. The formulations also provide excellent cleaningperformance.

Further improvements in RSS-24h performance can be achieved using alower HLB non-ionic surfactant such as Tristyrylphenol ethoxylate—6.5 EOinstead of a mixture of 8EO even when mixed with 4EO, as shown in Table5.1. Both Formulation G and Formulation H pass RSS-24h with 3.95 LR and4.18 LR, respectively, against E. aerogenes on stainless steel. Bothformulations are at pH 4.5.

TABLE 5.1 Components G H (actives) (ppm) (ppm)Alkyldimethylbenzylammonium chloride 4000 2500 (ADBAC) (CAS 68424-85-1)Dimethyldidecylammonium 1000 2500 chloride (DDAC) (CAS 7173-51-5)Mirapol ® HSC-310 1200 1200 Citric acid 2200 2200 Ethylenediaminetetaracetic 1500 1500 acid, Disodium salt (EDTA-Na2) Dodecylamine oxide(e.g. Mackamine ® 1350 1350 LA) Decylamine oxide (e.g. Mackamine ® 13501350 C10) Tristyrylphenol ethoxylate - 6.5EO 4500 4500 Water BalanceBalance Test Microorganism Enterobacter Enterobacter aerogenes aerogenesTest Substrate Steel Steel Log Reduction 3.95 4.18

To further evaluate the efficacy of the formulation with respect toantimicrobial performance [ready to use (RTU) application], FormulationH liquid was tested for Virucidal Efficacy against Human Coronavirus(ATCC VR-740, Strain 229E). For Viral Efficacy test, EPA recommends theAOAC Use-Dilution Test modified for viruses or the ASTM E1053. Theformulation was tested for 10 minute exposure time with an organic soilload of 5% fetal bovine serum. The recoveries were tested with WI-38(human lung) cell line. Complete inactivation of the test virus wasdemonstrated. A 23.00 log 10 reduction in viral titer was demonstratedper volume inoculated per well and per carrier (PASSED). All testcontrol results met acceptance criteria for a valid test.

The robust use of lower HLB non-ionic Tristyrylphenol ethoxylate wasfurther explored by reducing the “quat” concentration to less than 3000ppm while improving cleaning performance (Table 5.2). Reduction in“quat” concentration is desirable for improving the hazard profile ofthe formulation. Further improved cleaning performance is achieved by anoverall increase in concentration of surfactant, while increased polymerconcentration. Formulations I, J, K as outlined in Table 5.2, all passRSS-24H and provide excellent cleaning performance.

TABLE 5.2 Components I J K (actives) (ppm) (ppm) (ppm)Alkyldimethylbenzylam- 1450 600 2300 monium chloride (ADBAC) (CAS68424-85-1) Dimethyldidecylammonium 1450 2300 600 chloride (DDAC) (CAS7173- 51-5) Mirapol ® HSC-310 2400 2400 2400 Citric acid 4000 4000 4000Ethylenediamine tetaracetic 2200 2200 2200 acid, Disodium salt (EDTA-Na2) Dodecylamine oxide 4050 4050 4050 (e.g. Mackamine ® LA) Decylamineoxide 4050 4050 4050 (e.g. Mackamine ® C10) Tristyryl phenol 4500 45004500 ethoxylate - 6.5EO Water Balance Balance Balance Test MicroorganismEnterobacter Enterobacter Enterobacter aerogenes aerogenes aerogenesTest Substrate Steel Steel Steel Log Reduction 3.85 4.73 4.73

Performance in RSS-24h performance were also explored with variations inpolymer type. The polymer Mirapol®HSC-310 above is an acrylicacid/DADMAC co-polymer (anion-cation). Table 5.3 outlines use of 3 otherpolymers HSC-500 (polysulfobetaine), HSC-500 VPA (polysulfobetainevinylphosphonic acid co-polymer) & HSC-2 (ethyl ester of acrylicacid/DADMAC co-polymer). The HSC-500 (sulfobetaine) has a concurrence ofa cationic and anionic moiety, while the HSC-500 VPA has additionalphosphonic acid anions, and the HSC-2 has more hydrophobicnon-ionic/cationic character. Another commercially available form of theHSC-500 with added citric acid is outlined in the specification asMirapol®Surf 5500. At the use levels outlined in Table 5.3, when RSS-24hwas conducted with Enterobacter aerogenes on stainless steel,Formulation L shows 1.81 LR (98.45% kill), improving for Formulation Mto 3.15 LR (99.93% kill), and for Formulation N to 4.66 LR (99.998%kill). Formulation L, M, and N have pH 5.5, 5.5, & 4.2 respectively. The“quat” (ADBAC+DDAC) level was further reduced from Formulation N (5000ppm), to Formulation 0 (2900 ppm) and further to Formulation P (1000ppm). All the Formulations N, O & P are at pH 4.2. Even at 1000 ppm“quat” (ADBAC+DDAC) level, Formulation P shows “full kill” and >4.66 LRor 99.99% kill with RSS-24h.

TABLE 5.3 Components L M N O P (actives) (ppm) (ppm) (ppm) (ppm) (ppm)Alkyldimethylbenzylam- 2500 2500 2500 2300 200 monium chloride (ADBAC)(CAS 68424- 85-1) Dimethyldidecylam- 2500 2500 2500 600 800 moniumchloride (DDAC) (CAS 7173-51-5) Mirapol ® HSC-500 2500 — — — — Mirapol ®HSC-500 — 1300 — — — VPA Mirapol ® HSC-2 1600 2400 2400 Citric acid 200200 2500 4000 3200 Ethylenediamine 1500 1500 1500 2200 1100 tetaraceticacid, Disodium salt (EDTA-Na2) Dodecylamine oxide 1400 1400 1400 40504050 (e.g. Mackamine ® LA) Decylamine oxide 3100 3100 3100 4050 4050(e.g. Mackamine ® C10) Tristyrylphenol 6300 9400 5000 5000 3900ethoxylate - 6.5EO Water Balance Balance Balance Balance Balance TestMicroorganism E. aero E. aero E. aero E. aero E. aero Test SubstrateSteel Steel Steel Steel Steel Log Reduction 1.81 3.15 4.66 4.66 4.66

Example 6—Long Lasting Dilutable Concentrates

Formulations Q and R (Table 6) were diluted and tested for cleaningperformance and RSS-12h with E. aerogenes on steel.

The cleaning performance was comparable to other dilutable concentratebenchmarks at similar dilution factors. Table 6 shows 30× dilution of Qand R (Q-30× and R-30×, respectively) and further 60× dilution of R(R-60×). 100 microliters of the diluted compositions were applied onsteel substrates for RSS-12h. While Formulation Q is higher in totalactives compared with Formulation R (16% w/w), the RSS-12h resultsshow >3 LR for 30× dilutions and even for the 60× dilution ofFormulation R.

TABLE 6 Components Q R Q-30X R-30X R-60X (actives) (ppm) (ppm) (ppm)(ppm) (ppm) Alkyldimethylbenzylammonium 21800 18000 727 599 300 chloride(ADBAC) (CAS 68424-85-1) Dimethyldidecylammonium chloride 5400 4500 180148 74.0 (DDAC) (CAS 7173-51-5) Mirapol ® CP-412 22300 18400 743 613306.0 Citric acid 28600 23600 953 786 393.0 Glutamic acid diacetic acid,6900 5700 230 190 95.0 tetrasodium salt (GLDA) Decylamine oxide (e.g.Mackamine ® 40900 33700 1363 1124 562.0 C10) Dodecylamine oxide (e.g.Mackamine ® 40900 33700 1363 1124 562.0 C12) Tristyrylphenolethoxylate - 6EO 27300 22500 910 750 375.0 (TSP-6EO) Water BalanceBalance Balance Balance Balance Total Actives (% w/w) 19.41 16.01 0.650.53 0.2667 100 microliters Test Microorganism Enterobacter aerogenesTest Substrate Steel Steel Steel Steel Steel Log Reduction — — 4.58 4.284.06

Example 7—Improved Environmental Profile

In another embodiment, to further improve the environmental profile ofthe concentrates, formulations were adapted to reduce the hazardouscomponents. These compositions are shown in Table 7 as Formulations Sand T. DDAC was removed (more chronic environmental hazard) and ADBACwas used in a reduced amount (15900 ppm vs. 18000 ppm). Thesecompositions were then further diluted 30× (S-30× and T-30×) and applied(100 microliters) on steel substrates and tested by RSS-12h protocolwith E. aerogenes. These environmentally improved compositions passRSS-12h with >3 LR.

TABLE 7 Components S T S-30X T-30X (actives) (ppm) (ppm) (ppm) (ppm)Alkyldimethylbenzylam- 15900 15900 530 530 monium chloride (ADBAC) (CAS68424- 85-1) Dimethyldidecylam- 0 0 0 0 monium chloride (DDAC) (CAS7173- 51-5) Mirapol ® CP-412 22484 22484 749 749 Citric acid 19155 19155638 638 Glutamic acid diacetic 2900 0 97 0 acid, tetrasodium salt (GLDA)Decylamine oxide 33700 33700 1123 1123 (e.g. Mackamine ® C10)Dodecylamine oxide 33700 33700 1123 1123 (e.g. Mackamine ® C12)Tristyrylphenol 22500 22500 750 750 ethoxylate -6EO (TSP-6EO) WaterBalance Balance Balance Balance Total Actives (% w/w) 15.0339 14.74390.50 0.49 100 microliters Test Microorganism Enterobacter aerogenes TestSubstrate Steel Steel Steel Steel Log Reduction — — 4.09 3.26

Example 8—Non-Ionic Surfactants

Three nonionic surfactants were added to Formulation A at 0.5% activesto alter cleaning performance. The addition of alcohol ethoxylates(Rhodasurf® BC-630 and Rhodasurf® 91-6) to Formulation A did not improvecleaning performance. In contrast, tristyrylphenol exthoxylate 8-EOshowed a dramatic improvement in cleaning performance at the same uselevel (FIG. 7).

The disclosed subject matter has been described with reference tospecific details of particular embodiments thereof. It is not intendedthat such details be regarded as limitations upon the scope of thedisclosed subject matter except insofar as and to the extent that theyare included in the accompanying claims.

Therefore, the exemplary embodiments described herein are well adaptedto attain the ends and advantages mentioned as well as those that areinherent therein. The particular embodiments disclosed above areillustrative only, as the exemplary embodiments described herein may bemodified and practiced in different but equivalent manners apparent tothose skilled in the art having the benefit of the teachings herein.Furthermore, no limitations are intended to the details of constructionor design herein shown, other than as described in the claims below. Itis therefore evident that the particular illustrative embodimentsdisclosed above may be altered, combined, or modified and all suchvariations are considered within the scope and spirit of the exemplaryembodiments described herein. The exemplary embodiments described hereinillustratively disclosed herein suitably may be practiced in the absenceof any element that is not specifically disclosed herein and/or anyoptional element disclosed herein. While compositions and methods aredescribed in terms of “comprising,” “containing,” or “including” variouscomponents or steps, the compositions and methods can also “consistessentially of” or “consist of” the various components, substances andsteps. As used herein the term “consisting essentially of” shall beconstrued to mean including the listed components, substances or stepsand such additional components, substances or steps which do notmaterially affect the basic and novel properties of the composition ormethod. In some embodiments, a composition in accordance withembodiments of the present disclosure that “consists essentially of” therecited components or substances does not include any additionalcomponents or substances that alter the basic and novel properties ofthe composition. If there is any conflict in the usages of a word orterm in this specification and one or more patent or other documentsthat may be incorporated herein by reference, the definitions that areconsistent with this specification should be adopted.

What is claimed is:
 1. A hard surface treatment composition comprising:a. an antimicrobial component comprising at least one quaternaryammonium compound; b. a synthetic polymer comprising: i. at least onecationic monomer A_(b), ii. optionally, at least one anionic monomerB_(a), and iii. optionally, at least one non-ionic monomer C_(a); c. anorganic acid; d. a surfactant selected from the group consisting ofcationic surfactants, amphoteric surfactants and combinations thereof;and e. and at least one non-ionic surfactant selected from the groupconsisting of low hydrophilic-lipophilic balance (HLB) non-ionicsurfactants with a delocalized electronic structure that have moderateto poor water solubility.
 2. The composition of claim 1, wherein a filmformed from the composition kills at least 95% of microorganisms for atleast 3 abrasion cycles according to RSS-12h.
 3. The composition ofclaim 1, wherein the antimicrobial component is selected from the groupconsisting of monoalkyldimethylbenzyl ammonium salts, dialkyldimethylammonium salts, and combinations thereof.
 4. The composition of claim 1,wherein the monomer A_(b) is selected from the group consisting ofdiallyldimethylammonium halides.
 5. The composition of claim 1, whereinthe polymer comprises monomer B_(a) selected from the group consistingof acrylic acid, methacrylic acid, and combinations thereof.
 6. Thecomposition of claim 1, wherein the polymer comprises monomer C_(a)selected from the group consisting of 2-(dimethylamino)ethylmethacrylate (DMAEMA); N-vinyl pyrrolidone (NVP); N-vinylimidazole;acrylamide; methacrylamide; alkyl acrylate; and combinations thereof. 7.The composition of claim 1, wherein the organic acid is selected fromthe group consisting of citric, malic, maleic, lactic, succinic,glutaric, adipic acids and combinations thereof.
 8. The composition ofclaim 1, wherein the surfactant comprises a cationic surfactant selectedfrom the group consisting of cationic amine oxides.
 9. The compositionof claim 1, wherein the surfactant comprises an amphoteric surfactantselected from the group consisting of sultaines, taurates, andcombinations thereof.
 10. The composition of claim 1 further comprisinga polar solvent.
 11. A method of providing a surface with residualantimicrobial action that comprises the step of applying the compositionof claim 1 to the surface.
 12. A substrate with residual antimicrobialaction comprising a substrate wherein at least a portion of thesubstrate is coated with the composition of claim
 1. 13. The use of acomposition of claim 1 to substantially reduce or control the formationof microbial colonies on or at a surface.
 14. The use of claim 13,wherein a film formed from the composition kills at least 95% ofgram-positive bacteria and gram-negative bacteria, or enveloped andnon-enveloped viruses according to a modified version of EnvironmentalProtection Agency (EPA) Protocol #01-1A residual self-sanitizingactivity test.